CA2984432A1 - Composite thermoplastic polymers based on reaction with biorenewable oils - Google Patents

Abstract

Provided herein is a polymeric composition, comprising a random copolymer comprising three or more distinct monomers, wherein a first monomer is a biorenewable oil and at least one monomer has been polymerized into a thermoplastic polymer. Also provided herein is a modified asphalt for use in several asphalt end-use applications, comprising an asphalt binder in an amount ranging from about 60-99.9 wt%, an asphalt modifier in an amount ranging from about 0.1-40 wt%, wherein the asphalt modifier comprises about 1-75 wt% of a thermoplastic polymer and a remaining balance of biorenewable oil.

Description

COM POS1TE THERMOPLASTIC POLYMERS RASED. ON REA CTION.MITH
RIORENEWABLE OILS.
TECHNICAL FIELD
[0011 This. disclosure. relates to reacted and unreacted biorenewahle oil in combination with thertneiplagie polymer products that are mixed into asphalt to enhance performance of virgin as.phaltandior pavements containing recycled andlor, aged bituminous material.
BACKGR.OLJND
[OM] Recent technical challenges facing the asphalt industry, have created opportunities for the introduction of agriculture-based productS for the overall performance enhancement of asphalt.
Although therrnoplaStic polymers and waxes have been used in asphalt as modifiers to improve various aspects: .of performance, interesting synergistic benefits from the:
use: of composite modifiers containing thermoplastic polymers and bio-renewable.oil based prodtictS can lead to useful performance: enhancements. Such -performance enhancements may includefor :example but aretft limited to expanding the useful temperature index (UTI) of asphalt, rejuvenating aged asphalt. WhileirnprovMg -durability and toughness, and compaction aid applications in which the product can be used. to redneethe required compaction energy a' haul distance of the asphalt loose mix from the plant to the job-site.
.SLIMMARY.
[0003] ProVided herein is. a polytneriCtoinprisitions:coipprising three or More distinct Monomers that leads to the formation of a random copolymer, wherein :at least. one monomer is a biorenewable Oil and at least one Mottottier has been polymerized intoii thermoplastic polymer.
[0004] Also provided herein is a modified asphalt-tbr use in several asphalt end-use applications, comprising an asphalt binder ittan amountrangingfrom about:00-9.9..0-wt%, anasphalt modifier in an amount ranging from 00ot 0.1-4.04N, 'wherein:the asphalt modifier Comprises about 1-75 wt% of a thermoplastic: polymer and a remaining balance of biorencwable FIGURES
[0005] Figure 1 shows a comparison ofthe results:oftxample 1 terms of strain NReCOVery) after a I see 34Pa Creep loading using the Multiple Stress.
Creep. and Recovery Procedure-(MSC.R) procedure after blending. and after full, curing for 11 firs.
SUBSTITUTE SHEET (RULE 26) [0006] Pigott 2 shows a eOrripariSOn &the result of Example 2. ititeridsof ritrcerittif retoVerable strain -(%Repovety) after .8 1 see .3.;411a creep loading using the Multiple Stress Creep and Recovery-Protedure (MSCR)-procedure after blending and after full curing for 12.
[0007] Figtire 3: shows a comparison ofthe resultaof Exatriple3 in terms of percent OfreeOverable strain ("YqRecovery) after a. 1 sec 3,2kPa creep loadin using the Multiple Stress- Creep and Recovery Procedure (MSCR). procedure after blending and after -full Miring for 12 hrs.
[00M Figure 4 shews aeomparison of:the results of Example 4 in terms of percent of recoverable strain (%itecovery) after a: I sec 3.2kPa creep loading using the Multiple Stress Creep and ReeeVery:PrOcedure (MSCR).procedure after blending and after full curing-for 12 hrs.
WO] Figure 5 provides results of Example 4 in terms- of percent of recoverable strain.
(%RecoVery) after a I sec -3-.2.kPa creep loading Using the. Multiple Stress Creep and Recovery Procedure (MSCR) procedure, plotted against process tiMe(Blending/Curing);
[0.0010] :Figure. 6 shows a comparison of the results of Example 5 in terms-of percent of reecWerahlestrain(%Recovery) after a I see.3.2kPa creep loading Using the-MtiltipleStress Creep and Recovery Procedure (MMR) procedore after. blending and after full curing Ibis 1:2 hrs.
[000111 Figure -7 shows acomparison of the results of Example 6 in terms apeteetit of recOvtrablestrain ("4Recovery). after a I sec 3.2kPa creep loading using the:WI tipleStress Creep and. Recovery Procedure(MSCR) procedure after blending and after MI curing for 12.hrs.
[000121 Figure: 8 shows a CompariSon of the results. of. Example 7 in tertot- of percent Of recoverable straineARecovery).afier a 1 sec 3.21c.Pa creep loading using the..Nfultiple Stress Creep and. Recovery Procedure- (MSCR) procedure after :blending and after full curing for 12 hrs.
[00013] 'Figtire9 ShowS-the specific, heat of Me asphalt mOdifier described in .Exadiple: 8.
1000141 'Figure- 10. shows a plot.:ofthe complex modulus against temperaturefor -asphalt modified with the asphalt Modifiers described in. Example 9. Results show õthree temperature ranges of asphalt performance id-terms of modifier functionality and desired performance.
[00015] Figure 1.1 show.sibe:specific heat. of the asphalt -modifier:described-in Example 10, measured using a Perkin .Elmer _DSC:during a beating ramp. at a fixed heating rate of TOT/min.
[000161 Figure 12 shows a plot fete complex viscosity-against-terdperature.for asphalt Modified ivith the asphalt modifiers. described in Example 10.
[000171 Figure. 13 shows a plot: of the complex viscosity against temperature for asphalt:
modified with the asphalt Modifiers described in EXample 11.
SUBSTITUTE SHEET (RULE 26) DETAILED -DESCRIPTION
[00018]
Aspects described herein provide an asphalt modifier system comprising a biorenewahle .011-based product and wthermoplastin.polymer or wax (alga referred to. herein as "asphalt Modifier," 4-"blend:"--a"theritteplaStie polymer and oil bleildTeritodifier syStetii"...;
Methods of manufacturing, the modifier system. as: well as its incorporation into asphalt, roofing, and -Waling applications are:also described.
[00019]
value" is-define.d as. mass orpotassium hydroxide needed in ma to neutralize one gramatsample according to Aocg Cd 3d63. Acid value is a way of quantifying the amount of free fatty acid. in -4 sample and has.thennitstrig [00020]
mi value" is defined as the number of mg -KM equivalent to the basicity of one grain at test satripleatid has the units mg KOIlig.
[0002I1 .."01.1.goMer" is :defined as..--a polymer having a number average Molecular-weight (Mn) larger than 1000. A -"monomer:makes. up everythingelse and includes monoacylgyclerides õ(MAci), diacylglycerides (DAQ), triacylglycerides.(TACi."), and free fatty acids [00022]
"Reacted:" blends referto hiendsin which sulfur crosslinking and.
polymerization occurred prior to-asphalt addition.
[000211 "Unreacted." blends refer to blends- in which no Silitr cro-sslinking or polymerizationoccurred prior to asphalt addition..
[00024]
Also, .for purposes herein-, it -shall be understood that vtileardiation and.
sulltirization are used herein interchangeably.
Biorenewohlo Oil ASused herein,. '1,1-tirentwah1e-oi1e -can inehtdebils. isolated front- plait%
anititals..;
and microorganisms including algae.

Examples. of plant-based oils that may he. used include-, but: are not limited-to Soybean oil, linseed ail, datiola Oil, rapeseed Oil, cottonseed Oir,StitilloWer Oil, sith Oil, tall oil, peanut oil, safflower oil, corn oil, -corn stillage oil .(also known: as recovered corn oil) and corresponding. distillates and. fatty, adds, lecithin. (phOsphOlipidS). and combinations and ern&
streams thereof or co-products, by-products, orresiduesieSultingfrom oil refining processes.
[000271 Examples. of animal-based:ails may' include but are not limited to animal fat.
(e.g., lard, tallow), and. cOmbitiationS and crudeStrearnS thereof.

SUBSTITUTE SHEET (RULE 26) [00028]
Biorenewable oils can also includepartially and filly hydrogenated Oils, oils with conjugated bonds, and bodied Os Wherein a beteroatorn is not introduced, including;
diaeylglyeerides, morioatylglycerides, free fintyacids,.and alkyl esters of -fittty.acids-(e.g.7-methyl, propyi,:and butyl esters).
[00029]
Itiorenewable oils, can also include derivatives. thereot for example, previously modified,ratikally polyinerized, polymerizedõ orfunctionalized Oits(intentional or unintentional) wherein a heteroatom (oxygen, nitrogen, sulfur, and phosphorus) has been introduced may also be used asthe starting oil -material. Examplesortmiutentionally modified oils are used cooking oil, trap LiteaSe, brown grease, Or other used industrial oila. 'Examples of previOttsly Modified Oils are those that have been -previously "vulcanized or polymerized by other ip.olymerizing technologies, siich-aS Maltie anhydride or acrylic acid Modified-, hydrogenated, dicyclopentad iene modified, conjugated via reaction with iodine, interesterified, or .processed lo.. modify- acid value, hydroxyl number, or other properties. Such modified oils can he blended With unmodified plant-based OHS or animal-based Oils, fatty acids, glycerin, and/or gums material[00(KI In preferred weds, the biorenewable oil is:recovered corn oil (typically residual liquids resulting from the manufacturing process- of turning-corn into ethanol) or soybean oil. In another preferred aspect; the biorenewable oil is a free fatty acid. .0fle skilled in the art will recognize that if higher functionality is. desired, biorenewable oils having higher levels or unsaturation hi4 be used, Conversely, higher saturates may incotporated to further vary solvent parameters of thepolyinerized-ops to improve pertbrmanceproperties in asphalt.
ThOinptilOtte Polyiner (60.0311.
As used herein 4hermoplastie- polymers"- may include polymers commonly cliisaified as "elastoiners" and "plaStoiners" pre-polymers (such as thermoplastic resins), ()tipplers, and high. molockdar weight polymers. In one preferred aspect the thermoplastic polymer can. be a polyolefin oralnodified polyolefin. In other preferred aspects, a styrene-based elastotner is Used. In Other aspects the therinoplastic polymer maybe that which is contained in ground. tire rubber (Urn Examples of useful thermoplastic polymers for. 04-application are styrene, divinylbenZene, indene, or othervinyl aromatics, inch ding. styrene-based polymers such.
as st)rrene-butadiene-styrene (SBS) ProdUced by ).<4.4t.cii.l. and Priasol, and emulsified or non-emulsified styrene-;butadiene rubber; Reacted Elastomeric Terpolymers such as the tivaloy'rm KET produced by DuPont; and polyolefins such pOlyethylette, .pOlyPrOpylene... and.
4.
SUBSTITUTE SHEET (RULE 26) polybutylene, and .functionalized polyolefin such as the Titan rm plastomer produced by Honeywell.
[000321 As described above,- "thermoplastic polymers" may also include :waxes such-as polyamide wakes that .comprise a polyantine and a fatty acid, such as ethylene histearantide-and tristearamide.
Aphe0MOW if! r 47yslet WWI The-asphalt:modifier system. describedherein comprises a blend of biorenewable .911 aild.o.ffieritiopiastW, pillyther. Modifier systems in the Moran do not blend biorenewable oil with a. thermoplastic polymer 'but:rather directly add thermoplastic polymer to asphalt without additional materials or cOrtiponenta. It has b6ett-fetmd that-the blend of the present invention and its composition a.ceelerates dispersion and provides more uniformity When incorporated into asphalt, even with lower shearing and blending time requirements. compared to that-used in prior art systems.
100034] In conventional polymer modified asphalt (the prior art), the asphalt is heated to temperatures often exceeding I 50 C at-Whieh- OW the polymer is. added to the asphalt at the desired dosage. Since the polymer is often provided in. solid pellets, alengthy high temperature and high shear blending period is required-if) homogeneously distribute the.polVtier in the-asphalt.
For many styrene-based elastomeric modifiers, a second -stepis:ineluded in-the.prior art during -whicho cress-linker such as peroxide era sulfut.containingcompound is added to the blend and reacted for a few hOnrs..'Finally the asphalt aleing with-the .polyrner etmtittiteS to be. heated for an additional 1Z-1:5 hours: to ensure MI curing of the -polymer, during which, the. polymer swells throughadSorption of lighter fractions in-the asphalt.
[00035] The described Modifier system herein provides a polymer with enhanced .performanee characteristics (in :tams of elasticity and modulus): but with higher workability, and in some cases, lower melting:points. This ettablet-thetItelifa lower blending temperature, shorter blending times, and lower agitation levelsif necessary. Furthermore, the composite thermoplastic polymer described herein .oftendo. notteoire lengthy "curing' periods to achieve equal or better performance characteristics than that Of conventional thermoplastic polymers added using conventional -methodolow..
[00036] The blend of the present. invention can. be achieved through .direct reaction Of a thermoplastic polymeric material into a suitable, and in some aspects, reactive biorenewahle The blend often times comprises between about 1-75 wt% of a thermoplastic polymer with:the SUBSTITUTE SHEET (RULE 26) remaining balance beingbiorenewable oil. The upper limit Of the polymer is defined bythe target end-use asphalt application. Lower thermoplastic polymer dosages are used in eases when the end-use application requires higher workability or reduction of :production temperatures:.
Ftirtheritiore depending on the: end-use application. one May control the:
degree of *corporal:On of biorenewable oil into the thermoplastic pelmet For example,. in: the case of asphalt.
modification, addition .of the reactive polymerized biorenewable oils to the:
asphalt prior to addition of the thermoplastic polymer. results in an in-situ polymerization and reaction in the asphalt. In other examples, ,the degee of crosslinking in the thermoplastic polymer may be manipulated by controlling the level of croSSlifiker incorporated into thoerosslinked biorenewable oil. The-following paragraphs describe various aspects of this invention.
W0..71 Generally, the process to manufacture the asphalt Modifier system: of the present inve:40.4).n comprises first heating. a biorenewablo oil to a sufficiently high temperature. This temperature is in the range-of-8e to 1.50T for a s.uitable-waxy or crystalline polymers orpolyolefin (a suitable polyolefin will have A melting point above the pavement performance temperature range and below that.of typical :production-temperatures). For amorphous polymers such asstyrene based elastomers, the desired temperature Will.be at or:higher than the glassy or rubbery or a temperature sufficient: enough to achieve a reduction in cohesive 'forces. for -efficient diStribtttion in the oil meditim. Incases -where a reactive biorenewable oil is.uSed,..the temperature should be sufficiently high for the reactivity between the .biorenewable oil and the thermoplastic polymer. Tbe:Ahermoplastic:polymer is gradually added while maintaining.the temperature of the blend and agitated Until a tatifortn,:heinogenized:distribUtion in the biorenewable on medium is achieved.
[000381 Blending tinitis defined, as the time requited for -homogenizing. the polymer into the biorenewable oil. This Will often occur within 1 hour without the need for high shear Agitation.
For polymers such as styrene-butadiene- Kock -copolymers, high shear blendingnigy be used to accelerate the rate of polymer incorporation into the biorenewable oil, but is required.
[00039]
For polymers such as: .styrene-butadiene. block copolymers, a period of high temperature:curing may facilitate the swelling of thothermoplastie polymerthrough absorption of fractions in 'the biorenewable 01k:re:selling in improved -elasticity and an increase in modulus.
especially when used in asphalt end u.seApplieations.
[00040]
In another aspect,- the thermoplastic polymer may have: a high wax- content or crystalline fraction. In preferred embodiments, the :-wax has a. melting temperature higher- than typical asphalt end-use performance temperatures (Usually about 80 C) but lower than typical.
SUBSTITUTE SHEET (RULE 26) production .and Constioqiententperatures (usually about -135'C), This leads to a reduetion in viscosity in the. end use application when it is heated beyond. the melting point; enabling the reduction-of rt.-*Iiired product* and cOnstruOion teMperatures. Polycilefins such as polyethylene;
polypropylene, and: polybutylene are:well-suited to this application, [000411 In another aspectõthentodifier system:of the present invention May further include a erosslinking- agent such as: sulfur-contalning coMpounds. or peroxides added. after the homogenization of the polymer in the biorenewable oiL Anothercrossfinking agent that may be used is a sulfur-containing Compound in combinatien with a perOxide pot:phosphoric-0d, and super acid. catalysts.
[000421 Thetrosslinker may be fully or partially reacted with the.
thermoplastic polymer and the biorenewable oil, depending..on the stage at which the croSslinker is added to the blend, and the reaction time. Fully erosslinking can provide a continuous network of the elastomeric polythers across the biorenewable Oil Medium that will lead to enhanced mechatticaloteOlogiCali and damage resistance properties as needed in asphalt. applications and specifications.
[000431 In another aspect, the. cross linker is added:RA-le biorenewable oil before or at the time of the addition of the thermoplastic polymer.
[00044] in another aspect for asphalt applications; the crosslinker is not added:to the oil and polymer reaction, but is instead added: to the. asphalt blend comprising the blend for an in-situ reaction with the: thermoplastlepoly.mer-oll blend. Sufficient blending temperatures and reaction time would he required fOrfukreaction. Effectiveneu.ofthe:reaction inasphaltis often assessed by measurement of the elasticity Of the *Of With n-Pyitainic Shear-Rhetnneter;asstioWti in the examples.
[000451 In another aspect, a reactive biorenewable oil, preferably at least a partially sulfurized biorenewable oll may be. used, which contains reactive sulfur when heated to sufficiently high temperatures (about- 1:00 to 200"C4 but preferably between 185 to 195 C).
Addition of a thermoplastic polymer with .sufficient unsaturation can lead to reaction with the reactive sulfur inthe.oilsesulting in crosslinks of the reactive double bonds in the polymerized oil (may be in the fieelatty-acid,:MAG;.PAC4 TAci,-or any oligomer thereof)õ and the thermoplastic polymer as welt as .between molecules of the thermoplastic polymer. This will result :in an extremely Stable Conibined Modifier system as well as improved mechanical, theological, and .damage- resistance .properties. Thermoplastic elastomers such., as styretw-htttadiene-styreue are well suited for sueltan application.
SUBSTITUTE SHEET (RULE 26) [000461 The reaction between the biorenewable OIL thermoplastic polymert and optional crosslinkiag agent continues until:desired physical properties are met For -asphalt-modification, it . .
is desired to maximize the elasticity (e.g as measured using the DSR Multiple Stress-Creep and ReCOVery :prodedare) by increasing the degree of polymerization, - While.
Maintaining the workability a the-resulting thermoplastic.- polymer at temperatures lower than 190 C to enable efficient blending in the asphalt media *WO will place A. limit on the desired degree of polymerization.
gorp.Nry WWI gopto,s;
[00047]
For a-better understanding of the -variritiS embodiments described above, a -few exemplary embodimentsarehereinafter described, -The.m.Ost. preferred aspect includes reacting vulcanized biorenewable oil (wherein the biorenewable oil. is. vulcanized, using sulfur as described in co-pending provisional' patent application number 62f-126,064) with the thermoplastic polymer before incorporating the blend into asphalt Another preferred. aspect is incorporating the biorenewable oil and the thermoplastic polymer directly and individually -without reacting) into the asphalt and optionally incorporating a stall:if eroSslinker thereafter. Another preferred aspect. is. incorporating -both vulcanized biorenewable oil and the thermoplastic:polymer directly and individually into. itSphalt wherein the vulcattiied bloreneW ab e oil acts as a cross-linker carrier.
[000481 :As can be gleaned from the above description and the. examples below, the asphalt modifier system - comprises a combination -of-3 or .moremonoraers.-thatiead to:the:formation of random cOpOlyinersõWherein the random eOpOlytners include bittireneWable oils that. havebeen catioltically polymeriZeftusing:fironstcd acids. and Lewis Acids, including super acideataly.sis,-or sulfurization techniques. One ofSkill in the Art Will MO realize that the use of natural- oils, which coatti4- of fatty acids, possessing monounsaturated and polyunsaturated fatty acidS, lead. to the formation of hyperbranehed polymers.
Enck,Z1,*4pplieNtiops [00049]
For. the. purpose of this invention, asphalt, asphalt binder, and bitumen refer to the hinder phase atan asphalt: pavetilent:.13liijtaiaoas material may refer to a blend of .asphalt binder and other material such as aggregate artiller: The binder used in this invention-may be material acquired from asphalt producing refineries,- fltixi refinery vacuum tower bottoms, pitch, and other residues of processing of vacuum tower bottoms and. solvent-de-asphalting processes, as well as SUBSTITUTE SHEET (RULE 26) Oxidized and aged asphalt from. recycled bituthinotts Materialsuch as reclaimed asphalt paVenient -(RAP), and recycled, asphalt shingles (Itik),.
[00054 In one aspect, the present invention :provides-modified asphalteomptisinga blend of 60 wt to. to. 99,9 wt% of asphalt binder and 0.1 wr.A.-tO 40 wt!'..44...of the asphalt modifier. The modified asphalt may be-us.ed for road paving or roofing applications.
:Additionally, modified asphalt can be Used in :a Variety of industrial applications, not limited to coatings, drilling applications, and lubricants, in another aspect, the present invention provides:a modified asphalt comprising a blend of 60 wt% to 99.9 Wt% asphalt binder and (ii Wt% to 40 wt% of the asphalt -Modifier,: and one or more of the biorenewable oils described above, for example unmodified plant-based oil, animal-based oil, fatty acids, fatty acid Methyl esters, gums: or lecithinõ:and gums or lecithin in modified oil orother oil or fattyacid.
[000521 Other components, in addition to the asphalt modifier described in this:
invention, may be combined With, the. asphalt binder to produce aModifi0 asphalt for example: but not limited :to,. thermoplastic elastoineric and plastorneric -pcilymers (Styrene butadiene: -styrene, emulsified or non-emulsified ..styrene-butadiene rubber, :ethylene vinyl acetate, functionali2ed polyolefins, polyphosphorie:acikanti.stripping akiditiVes. (*nine-based, phosphate-based, etc.), warm mix additives,. emulsifiers, and 'fibers. Typically, these components are added to. the asphalt binderipolytterited-Oitat doses ranging from about 0.1 wt% to about -10 wt 4:
21 Modtficarion [00054 The:declining quality Ofbitittnen drives the need for-adding chemical modifiers to enhance the quality of asphalt products. Heavy mineral oils from petroletuniefining are: the most coin-Aim* Used modifiers.
[00054]
Mineral flux. Oils, petroleum-based crude distillates,: and re-refined mineral oils have been. used in attempts to soften the asphalt. Oflen,.useof such material, results in a. decrease of-the:high temperature modulus Or asphalt more :than the IOW teitiperature, tnakitigõ:the asphalt more prone of rutting. at high temperatures. Such effects.- result: in the reduction of the Useful Teraperaturelndex-(15M
[00055]
'Mineral. flux oils, petroleum-based .crude distillates, and re-refined mineral oils often have volatikfractions at pavement construction temperatures. (0.gõ 154) to I 80 C), generally have lower flashpoints Than that OfaSphalt, and i:pay"--b0-.pronetO higher loss of performance due to oxidative.aging, SUBSTITUTE SHEET (RULE 26) [00056].
The thentioplastic polymer and oil blends deSeribed herein are not only viable substitutes for mineral oil, but have also been shown to: extend the. un of asphalts to a greater degree than other performance modifiers,. therefore providing! -,=Itibstattrial value to asphalt enanufactUrerS. The observed increase in 1)11. Using the blends described herein is a unique property not seen in other asphalt softening additives such as asphalt flux.
filet oils, products based on aromatic ornaphthenic distillates, or Thigh. oils. Typically one grade itnprOventent in eitherthe StIRP:Performance-Orading(PG) specificatienor the Penetration grading system used in many =countries is achieved with approxiinately 2 to...3 ofthe blend by weight of the asphalt, for example, the increaSein V.TI seen for approximately by:Weightaddition of the. asphalt modifier can he as much as 4 C, therefore-providing a broader PG modification range such that-the lower end temperature can be lower without sacrificing the higher end temperature:
ikiztvexation-of Aged Bfrominous-Materia [0005:7] -Asphalt 'ages" through a combination of mechanisms. - Mainly o*lation and volatilization. Aging increases asphalt modulus, decreases. viscous:
dissipation and stress relaxation, and increases brittleness at lower performance temperatures._ As--a resultõthe asphalt becomes more susceptible to cracking and damage accumulation The increasing usage of recycled and reclaimed bituminous materials which contain highly aged asphalt binder from sources such as reclaimed asphalt pavements(RAP) and recycled asphalt Shingles (RAS) have createda necessity for "rejuvenatore capable of partially or completely restoring the theological and durability of the aged asphalt. The use of the thermoplastic polymer -andoil blends described herein, are Oarticularly usehil thr RAP and R.AS --Oplications as they eon-thine the. rejuvenating effect of oil component with the.toughening effect of the-therrnoplastic polymer incorporated into the blend.
[000581 Accordinglyõ. the Thermoplastic polymer and oil blends described herein have been shown to be capable a rejuvenating and toughening the aged. asphalt binder,-and restoring the rheolOgieal properties Of a lesser .aged asphalt andenhaticiag the durability Ofthe..hiriderv AS a result, small dosages of the blend can be-used to incorporate high contentof aged: re.cycled: aspha It material into -pavements and other applications -resulting in significant --economic saving and possible real** in the environmental impact of the pavement through reduction of use: of -fresh resources.
:1.0 SUBSTITUTE SHEET (RULE 26) Replating-Cottional Use] of ThOritioplastiePaymer in Asphalt [000.591. : Asphalt-is-often modified with thermoplastic elastomerie and plastomeric polymers such as SlyrerterButadiene Stvre ne (S8S) as well as ground tire rubber to increase high temperature Modulus-and elaSticity, to increase resistance to heavy loading, and toughening the asphalt.. matrix against damage accumulation through repetitive loading either through traffic on pavenients, or environmental and thermai effects in roofing applications. Such polymers are usually used at 310.7 wt% dosagesin the asphalt and can be as high as 20%. for ground:tire:110%er.
100666] -Conventionally the. .polymer is high- 'shear blended. directly' into asphalt at temperatures often **ceding. 1.$0 C.-and.allowed :.to "Ctirer.at sim.ilartemperatureS during Which the polymer- swells by 'adsorption of lighter fractions in the asphaltuntil a continuous volume phase is achieved in theaSphalt.
1000611 The: volume- phase of .the fully cured polymer -v411. be affected by degree -a-coinpatibility Of The polymer in the asphalt and thelinertea5ofthe dispersed particles resulting in an increased specific area and enhanced swelling potential through increase:
of the interface surftice between asphalt and polymer.
1000621 The thermoplastic polymer. and 00 blends described herein can be added -directly to the asphalt to achieve superior mechanical and.rheolo.gical properties duetothe higher polymer dispersion .and compatibilization in the Oil medium and consequently .a More efficient network.
formation in the asphaltemnpared to the conventionally used thermoplastic polymers.
[00663] .Furthermore, the thermoplastic :polymer and:oil blend -does- not-require- lengthy blending. time or:during periods after adding to the asphalt to aChieVe..and exceed the mechanical propertiesofasphakblends made using the conventional polymer modificationmethod described In. abOVe:
Compaction Aid Additivoloy tise in Asphalt 1000641 Asphalt pavements require a Minimum amount of energy to be produced and compacted. This ertergyis provided: through a combination of heat and mechanical energy through use of roftercompactoM Thus additives allowing for reduction in the required compaction energy to achieve target mixture density Can enable a reduction :-of the compactor.
passes or the -temperature; thus enabling an increase in the maximum haul distance of the asphalt mixtureliom the:plant to the job site.
[00005]. The:different mechanisms-through which such compaction aid -additives function may include increased lubrication fagot:gates. during asphalt mixture compaction, reduction of II
SUBSTITUTE SHEET (RULE 26) the binder viscosity at production temperatures, and better coating and *friability Of the aggregates.
[00066] The thermoplastic polymer and oil blends described herein can be used as a compaction aid, .0 achieve- a decrease -in the required compaction energy through increase in aggregate lubrication and aggregate wettability, as well as decrease in viscosity at the higher temperatures used during -cOnstrtittion. when the: thetinoplastic polyntef has a melting point in the range of 80 to.135X1lexample of which:is:a- suitablepOlytilefin such as polyethylene; oxidized polyethyleneipolypropylerte,-- and polybutylene), In such an Vplicatiorithe additiVewetild be used at dosages -preferably in the range of between about 0.1 and 2% by weight ofthebitumen, EXAMPLES--00061 for purposes herein, natural oil-based -"oligoinerrlS defined as a polymer Wing a number average molecular weight (Mn) larger than 11000. A monomer makes up everythingelse and litchi-deg m.ontutcylgyclerideS (MAG)-; diaCylglycerides.-(DAG)i triacylglyteridesi-(TAG)õ- and free fatty acids. (F.F.A.) Molecular weightis determined using:00 :Permeation Chromatography techniques..
:Example I: USeof Sanitized Vegetable-Based Oil as Polymer Compatibilizer and Cross-Linker [00068] Two 'polymer in asphalt blends were compared, one: in whiCh elemental sulfur- was added directly to---the asphalt to cross link the SBS following a conventional asphalt.
polymer modification procedure (Blend A), and the other in which a sanitized vegetable based oil with no CrOss linkerWas added to the asphalt-W.0101e addition of the [00069] The. Multiple Stress Creep and Recovery procedure under. AASHTO
n50 is a procedure designed 'for measuring theElasticity Of asphalt binders through repeated 1 See Creep and 9 see recovery steps, This procedure is. especially useful for assessing the performance of polymermodified.nsphalt Using the; strain response from the creep and recoverysteps a percent recovery.(%10-is calculated as. tt Measure of the ratio of the recriverable strain daring, the. 9 see recovery period to the total strain imposed by Me:endof the 1 sec creep step.
By nommlizingthe strain at the end of the creep periodtolheimposedstress a compliance value -can-be measured (1).
The compliance corresponding toile:remaining strain at the end of the recovery period is referred to as the non-recoverablecomp1iance(114. An effective tlastomeric modifierwouldinerease the % Recovery, and decrease the:Jo:
[00070]. Blend A is a modified asphalt binder comprising:
* 94.58% neat asphalt binder graded as PG64-22 -(P0-05;7-249)]byWeight-of the-blend.

SUBSTITUTE SHEET (RULE 26) = 4,2% Of refined soy bean oil:by Weight:of the blend.
0, 12% Styrene-Butadiene Styrene (Kraton 0-1192) by weight of the blend.
= 0,021% of elemental Stii fur by weight of the blend.
[000711 Blend B is a modified asphalt binder comprising;
= 94.6% neat asphalt binder graded as P064-22 (PG 0.744,9) by weight of the blend.
= 4.2% of a polymerited vegetable,baSed oiL, As described betaw:
:60% by weight of g sulfurized refined soy bean oil reacted with 7.0% by weight of elemental sittfax At 1:75PC for 33 firs under a Nitrogen sparge. This resulted in a Modifier with 70,0% oligamers. -h. will be hereby referred to as VSB070.
a 40% by weight of refined soy beam oil o Blend of V$13070 ,and the unmodified Oil had a 45% oligomer content it will be hereby referred to as VS8045.
= :I I% of Styrene,-Butadiene Styrene (Kraton Dµ1192) by i.veight of the blend.
Blending Procedure:
1, The oil was blended into the asphalt after the binder had been annealed at 150 C. for 1 hour;
The modified binder heated tO abant 193 C for polymer modification

2. The RPM in the high shear mixer was set to:1000 while the SEiS was: added (within minute). Immediately after addition of the polymer the RPM was briefly ramped up to:3000 rpm for approximately 10 minutes JO insure full break down of the$BS pelletS, after *Wit the shear level was lowered to WOO rpm,

3. Polymer blending was continued at 1000 rpm for a OW of 2 hit,

4. if across linker step is needed, the temperature was dropped to about 182 C ata 150 rpm at Which point the sulfur cross linker was added. Blending was continued at 1:82 C and 150 rpm for 2 hrs.
S. Samples were taken from the Polymer modified hinder before and after it was placed in an oven at 150T for curing for approximately 12 hrs:(oVernight) to achieve full swelling of*
polymer.
[007.21 Performance grade tests were performed in accordance to AASHTO
M320.
Multiple Stress Creep and Recovery tests Were :performed on the imaged binder at 34 C in accordance to AASHTO T350. Details are shown in Table 1:
.13 SUBSTITUTE SHEET (RULE 26)

5 Table I
Blend -Conditions = = -%fteeovery Cross- Blend 1N, Binder:Name linker k:74'i'= Time SRSI"" .3 2. kPa: .at kP
Added Ratio. a.
P064;;22 +.4B0 Yes 0-22 OAS 24.78 4 hours t 0,02%S. Yes Yes 022 0.I.22 29.72 PG64-22-4,4230/0045 No No 0,22 0:128: 28.97 1 r 1,2%S.BS hour.
No Yes 0:22 0.1.0 3744 POP7.3.1 The results show that not only did use. oftbe stilfurlzed vegetable based oil eliminate the need for a Cross-linker by:delivering superior elasticity andeompliance at the conclusion of blending, if alsOdeVelOped a moreefficienfamihigher elasticity elaSto.meric polymer compared to the binderthat did not contain thesulfurized modifier at the conclusion of the curing step. Thisetin significantly:Simplify the mOdification process for the end- gOeri as handling of elemental sulfur and addition of a cross-linking step in unnecessary. As a result of eliminating thecrosslinkingstep the blend time was significantly reduced from 4 hrsto I hr.
1000741 By eon-1min the results of Blend B to that of the. conventional blend (Blend A) it is observed that theme of the- reactive sulfgrizedoileliminated the need for the 12 hr curing period by deliveringnearly -equal perfinithance after-only 1 hr of blending.
Example 2: Use of saltbrized vegetable-based oil as polymer compatibilizer and cross-linker:
[000751 Tw.o polymer modified asphalt blends were compared, one in whiCh elemental sulfur was added directly to the asphaltto cross linkthe S.B.Sfollowing a conventional asphalt:
polymer modification procedure (31epdA),00:the other in whith a.sulfgrixed vegetable based oil with cross linker was added :to. thensphalt before addition:of thepolyiner (Blend B).
[000761 Blend A is a modified asphalt hinder totnprising * :95.56% neat asphalt binder graded as PG644.2 (P0:(i57,.24.9) by weight-ofthe blend.
= 41% are:fined Soy bean oil by weight of thebleiid..
= 014% ofSty.rene-Butadiene Styrene (K.raton D- I 192) by-weight Of:the Wend.
041043 ofelemental sulfur by weightofthe blend.
[0.0077] Blend B is a modified asphalt binder comprising:
95.56%. neat asphalt binder graded as P064-4 (PG 65,7-24.9) by weight of the blend.
.1.4 SUBSTITUTE SHEET (RULE 26) wo 2016/196155 =
4:;2,4 of .$0ft.ii.O(Yiefined Okinier01. sulfur:
1.75C. f.ir 33 hrs ander-a Thi...ulted n a inodifiOr With 70,0%
Otigenter* 1 will be her0b.y.O.fefrOl.W44 VSB.070.:
0a4%.0fStyrent-Buta4itnt,:Styftilo..(KreOn 1.),-:;1,192):by.weight of the blend.
fltending:PrOt L The oi .8.va$ bion de d:itnO theii$11Mt ailet the bitiOer. had been.
annealed at I ' C. for 1 hour 'The:modified binder heated to about 193=T lOt polymer modilic4ou,:
Tbe RPM itithohigh shear 'Mixer v.Vas::..$0. to 100(l. wbile.tbe::$13$. was acidet.(WitliM
mnligo.), .4n ingaipi,ely 0*..a.*.ndon oft, polymer th RPM was h icti rarnpd ap..t0.300Ø
rprn lOtnnptOldtrintely.:10:nlintiteMitt8Ote.
iiiiibreakAowitofthe:SHS:pefletµafter vhieh the.0*0100u..w.4$3 iiiwe re dto 000 rpm 3. .Potywrimending.was.vontintwd:0:1.00.0:tpm fpr.a.t.O.tatot2 4...tra:.:etn 's la:Att.:step: is:need ec4 thO:telnpera cuit:*0 .dropped to about I.50,1-prItat ly.fkbpoluttflo:01Thr..croAs..litiker.was....044.e0, Blending.W5.,c9ntitmedat.
182CC and 150.
itOM
,S:igtip les '.ere taken from: lbe..?Olymer wo4ified::.birKlerbefore: and.
after :it was ritaco4;ikan :OVen: at 150 C ibrturing.for. approkimately.t2hts.OVernight) tvaehieV.01111.swellintol the Rt007.81 .:PerfOrtnande: 'grade tests , were performed trt aeeordan00t /NAW.17.0 M3 20:.
Jiiple $tivs$: Creep and :Recovery test*.:. were ..perffortned: on the onaged.
Nader at =ii.:4"c:.
.40etirdatteet0..AANtIT.0730:.:Potai.1.,$: are:$hown...inTnOleõ2;
=Table Blend Conditions = %=Rovt = ==- .
'Blend in, at .3' 4C. = = =
lainder NatO . :at 34--.C.3.2 'Hoke:* = = .11-ttic = 3.2 kl'ia Curin2. Ratio Id Added Yes, NO 0,05 VI. 14.23 P664,72 4-4.2%SBO
- .4 tiottrs .-0.24%Sf3S 0,0200Sc. Yes Yes 0,05 0,17 17.40 KiC422 . .0,05 0.15 211.0u37 No Yes 0.05 0.13 17,35 SUBSTITUTE SHEET (RULE 26) [000791 The results show thatuse of stilfurized vegetable based oil eliminate the need for a cross-linker by delivering equal elasticity and performance at the conclusion of blending and curing, thus significantly -siniplit4n.g.the MOdllication.prOcess for the end user.
Furthermore, as a result .ofeliminating theerosslinkingstep the blend time was Significantly reduced from 4 :hrs to 2 hr.
Example. 3: Use of .sulfttrized veuetable-based oil as polymer compatibilizer and cross-linker:
[000801 Two polymer Modified asphalt blends were tompared, one in Whicheleinental sulfur was added directly to the asphalttoõcross link the SlIg.fhllOwinga conventional asphalt polymer modification procedure (Blend A). and the other in Which a sulfuriZedvegetablebased oil while no:croSs linker was added to the asphalt before theaddition of the polymer (Blend 0).
[000811 Blend A is a modified asphalt hindercomprising:
= 95..56% peat asphalt binder graded aap06442 (PG (5..7-24.9). by weight of the blend.
.-* 42%:of refined Soy bean Oil by weight-oftheblend:
= 0.24% of Styrene-Butadiene.Styreno (Kraton D-1492) by weight of the blend.
= 0:0044 Of elemental suiflirby *eight of*. Wend, [00082] Blend B: is a modified asphalthinder comprising:
= 9556%.beat asphalt-binder graded apG6+!22. (PG 65;7-24.9). by. Weight Of the blend.
= 4:2%..ofaptilymerized vegetable-based oil (containing 0.0018% sulfur by weight of the asphalt), as described below:
Q.: -60%-by weight-of a sulfitrized. refined soy bean oil reacted with 7.0%-hy-weightof -elemental sulfur at, I-75T for 33 firs under a Nitrogen sparge. This4esUlted modifier with 70,0% oligoiners. It will be hereby referred to as V$B070.
4.0% by Weight oftefined soy bean oil 9- Blend of VSB07,9 and, the unmodified oil had a 45% oligomer content. it will be hereby. Werra:to as-VS.130,M
= 0,24%of St yrene-Elutadiene-Styrene:(Knnon D-1.192) by weight of the blend, Blending Procedure:
1õ The oil was blended into the asphalt after the hinder hadbeen Annealed at 150 C for Mow.
The modified binder heated to aboat I93e- for polymer SUBSTITUTE SHEET (RULE 26) 2. TheRPM in the high shear mixer was set to.-11:000-*hile theSBS was added (Within I
minute), hruncdiatelyatier addition of thc polymer the RPM was briefly ramped up to 3.00.0-.rpm for approximately 10 minutesto insure fun break down of theSBS:pellets, after which the Shear. level was lowered to 1000 rpm.
3. Polymer blending was continuedat. I00Ø.rpm fora total 42 hrs.
4. Ha cross linker step is needed; the temperature was drOpped to about 1.82 Cata1.50.rpth at which point the Whir:cross linker was added. Blending was continued-at I 82:',-C and I:50 rpm for 2 hit-S. Samples were taken from the Polymer modified hinder before and after it was placed in an oven at 150%7 for curing for approximately l2 hrs (overnight) to achieve full swelling of the polymer.
[000831 -Performance grade teSt.S were performed in accordance to AASHTO
M320.
Multiple Stress Creep and Recovery tests- were performed on the imaged binder at We in accordance tO AASHTO T359õPetalls are shown in Table 3:
Table 3 ;Blend:Conditions .
-%gepoverv 12hr SBS. 01 Cross- Jo at 34(1..:, .at 340C 3.2 linker = Time i0 .kPa - 34 kPa '==
.CurIng Itat Added =
=
PG6442.-+4,2%S.B0 Yes NO 0.05 0.21 1423 4 hours 024%03 + 0.020AS- Yes yes: 0.05 0,17 1740 No Sn 0,05 0,16 15-76 PC164-22 +42WVSB045-4..
'I hour-0.7.4%.SBS- No Yes 0A05 0,12 19.01 (00084] The results show-that use ofthe sal:IVO:zed vegetable based oil eliminated the.
need for a cross-linker. by-delivering a: superiorelaSticity and performance at the. conclusion of blending; Furthermore, the total sulfur present in the anifinized vegetable oiqof 'WO .Q.14 a.
thetion-j$ leaetiye at theblendcouditionS) was less than half of the elemental sulfur emsaiinket added to.the asphalt in Blend A., thug highlighting the much higher effitioney ittitoSslinking achieved-when the sulligized oil is used as a replacement: 11:g use of elemental sulfur asa crosslinker.

SUBSTITUTE SHEET (RULE 26) 100085] The results also signify-thM thenSe Of the sulfurited oil developed a. more effidientand higher elasticity elastotneric polymer compared- to-the ;bind:et that did .noteontain thesulfurized modifier at. the conclusion of the curing step. Furthermore, as a result of elitninating the trOSstinking step the blend tune was signifteatitly reduced from 4 hrsi to. I ht..
Example 4: Use of Reacted Vegetable-based Thermonlasfie 'Polymer ba.sed.:on Soybean [000861 Two polymer modifiedasphaltblends were.comparedõ one in which elemental sulfur was added directly to the asphaltto cross link the S:155:f0llowing a conventional asphalt polymer modification procedure (Blettd-A),..and-the Other in which a reacted St3S-vegetab1e based: oil blend was used as a thermoplastic polymer replacement and the only additivelBlend B).
[(/µ$)S7] Vend A is a modified asphalt binder-comptiSing;
:* 95.56%1101 asphalt !binder graded aS.:PG64-22 (PG 65--.7,24.9) by Weight-of the blend.
= 4.12% of refined soy bean oit brweightof the. blend.
= 9..4% of-Styrene-ButadieneStytene (Knit-On D41502). by wow of the Wend, = 0.004% of 'elemental sulfur by weight.of the blend..
1000881 -Blend B is a modified asphalt bindet-Coniptising;
= 05.56% neat asphaltbinder graded as -PG64,-.22 (PG 65;7%24.9). by weight.
of the blend.
-= .4A4% of.arsacted thermoplastic polymer blend (containing 0..9(129%
sulfur by -weight of the-asphalt), as:described below:
0: 15% by weight of a sulfittlied refined soy bean oil reacted with.7.0% by weight of -elemental sulfur at 175T for 33 tits under a Nitrogen sparge. This resulted in a modifier With-7Q.9%.011gomers-(VSB070).
-5%-byweight-of Styrette-Butadiene Styrene (kiaton t)41.9.1).
0: TheySt1070 was heated to 195T under light agitatiottatWitich point the 0-$13S was gradually added and continued .to be reacted .for 60 minutes after Which the reacted blend was tooled.
Blending Procedure:
Ish.e.ttil was blended into the asphalt aftcr. thebindet..bad been annealed at 1-5.Qae -fort hour.
The: modified binder heated to about i9PC'forpolymer modification.
-The.RPKinthe-high shear mixer was. set t4,1000 'while the..SBS was added (within. t minute): Immediately after addition of the polymer the RPM was briefly ramped up to 3000 SUBSTITUTE SHEET (RULE 26) rprn-forapprOtimately 10 minutesto insure full break dOwittiftheSRS
pellets,,after-whith the shear level was lowered to 1000 rpm.
3. Polymer blending was continued at 1000 rpm for a totatal hrs.
4: [fa cross linker step is needed, the temperature was dropped to about 182 C
at a 150 rpm at which point the sulfur cross linker was added. Blending was continued at 18240-and 150 rpm for 2 hrs.
.Samples were taken from. the Polymer modified .hinder before and after it was placed in an ,oVetim 150 C for curing for approximately: 12hrs (overnight) td-achieVe full Swelling of the polymer.
1000891 'Multiple Stress Creep and Recovery tests Were performed on the unaged binder at 34 C in accordanceto-A-ASHT01350. Details are shown in Table 4:
Table 4 Blend Conditions -Mtecovery Cross- Blend jorat. 34'=V =
BiodeNarne 12.11r. SRS/0i1 ' 3.2 linker . Time. 3:2 .kPa. =
Curing -.Ratio.kPi Added P6541,22- +4.*S.1101- Yes No 0.05 0.21 14,23 4 hours 0.24MBS. 0.02%S.- Yes Yes 005 0.17 17.40 P.06442 +4,4414i(VSB070,BS No No 0.05 0.10. 22,14 1 hour 95:$)No Yes 0.05 0.09 23.38 [00090] The results show a significant: increase in elasticity and creep stiffness (reduction increep compliance) with thenSe.Ofthe.reacted vegetable oilSOS thermoplastic polymer in.
place of conventionalõSOS modification., even though the SOS content of theasphakbinders remained unchanged. Ftirtherrnote,-uSeofthe reacted vegetable .oil-SOS.
thermoplastic polymer eliminated the need for additienof a cross-linker. This can significantly improve and simplify, the modification process for the end user, as-the-use of three additives.
(oil, SOS, and sulfur) is reduced to a single step modification with enhanced. performance that. re-quilted less thanhalf of the blend time of the conventional blends-:(1 hrs instead of-4 Example 5: Use of ReactedNeeetable-based Thermoplastic Polymer based on Soybean Oil #2:
1000911 Two polymermodified asphalt blends were compared, one in which elemental sulfur was added -directly 'tn-the asphalt' to cross link the SOS following acenventional asphalt SUBSTITUTE SHEET (RULE 26) polyther modification procedure (Blend Al), and the,other in which a reacted SBS,vegetrible based oil blend was used as a thermoplastic polymer replacement:and-the only additive (Blend B), [0100.921 Blend A is a modified asphalt .bindertotnprising:
o 94.58% neat asphalt binder graded as..P064-22-(PG.65.7r241.9) weight ofthe blend.
= 4,2%-of refined soy bean oil by weightof the blend.
Styrene,Butadiene Styrene (KratOn D-1192) by weight-Of the blend.
= 00.2% ofelemental sulfur by weight oftheblend_ [00093] Blend 113 is a modified- asphalt binder comprising:
= 94" neat asphalt binder graded as P064-22 (PE.i. 65.7214,9) by-weight of the blend.
= 51.4% of a:reacted thermoplastic: polymer blend (containing 0.001 it%
sulfur by weight of the asphalt), as described below:
o 78% by Weight:Of a:sulfitited refined-soybean Oil reacted with 710% by-Weight of elemental sulfur at 175 r for 3.3: hrs under a 14.4itrogen warm This resulted in a.
modifier With .70,0%-dligonters blended back With refined SBO 0445% HOMO:
content (VS$0.45).-o 22% by Weight of Styrene-Butadiene Styrene (KratonD,11.92) o The:VS:BEMS was heated to -1:95T under light agitation, at which point the D-1192 .S.BS was gradually added and Confirmed to be reacted for 60 minutes after which the reacted blend was cooled.
Blending Procedure:
I. The on was blended: into 'the asphalt after the binder hadbeen annealed at 150 C for I. hour (Blentl.A only), The MOdifiedbindetheated to about 193 C for polymer modifieation 2. The ROM in thehighshear mixer was set to 1000 while the .S.BS was added (within I
minute). Immediately after addition of the Writer the RPM Was briefly'ramped up to 3000 rpm for approximately 1Q,m.inuxçs to insure -MI breakdown of the .S13$.pellets, after which the shear level was lowered-t 1000-rpm.
3. ['Clymer blending was continued at 1000 tot for a-tOtalOI-2 -4. Ifacrosslinker step is needed, the temperature was dropped to about 1.82 Cat a 150 -rpm at point' the stair erriSs.finker was added. Blending Was:cotitinited at 1.82-feand 150 rptn hrs.
SUBSTITUTE SHEET (RULE 26) 5. Samples were taken front the Polymer Modified binder before. and diet it was placed in an oven at 1.50 C Or curing :for approximately 12-Ihrs (overnigbt)-toltievc, full swelling of the polymer.
[000941] Performance grade teats- were performed in accordance: to AASIITO
M320.
Multiple Stress Creep and ReedVery testa Were performed on the unaged: binder at We in accordance -to AASIITO T350. Details areshownin Table Table Blend-Conditions -%Recoverv Creas- Blend. 34T, =
Binder Name 121it $.1,1$1011 , .at.3VCõ.3.2 linker Time = 43:4.,'Kra kolt=.
Curing Ratio Added Pt364-22+41-2%Sig)-4 1:2.11*S-BS Yes No 0;22 0128.
28:917.
4 hour +002%$ Yes Yes 012 0;122- 29-.72 No No 0.22 -010 2:7.40 . . .
P064,22- +5414( VSB045-S BS
I hour M22) No Yes 0.22 32.81 [00095] The results show a significant in-Crease in elasticity and Creep stiffness (reduction compliance) with the use of the reacted vegetable-a-SBS thermoplastic polymer in. place of conventional SOS modification, even though the -SUStonteritofthe asphalthinders-remained unchanged: ftirthettnore, use of the reacted vegetable Oil-S.BS
thertnoplastiepolyniereliMinated the:need-for addition:Iola cross-linker. This can significantly improvennd simplify the.
modificationpiticess for theend user, as the use of three additives. (oil, SUS, -and-sulftn) is reduced to a single step modification with enhanced performance that only required less than half ofThe.blendtime- of conventional blends:
e Com = tit 11:(.! tt), a '= p ) [00096] Two polymer modified. asphalt blends were compared in Which univacted and reacted sfis.yegctabk based oil blend was used a n-thcrmoplaStic-polymerfoPlacement and the only additive (Blends A-and B).
(900971 Blend A is a modified asphalt hindettornpriSing:
= 94.0% neat asphalt binder graded as PG64-22. (Pa 0.7724.9) by weight of the blend.-SUBSTITUTE SHEET (RULE 26) = 604of areacted-therrhoplastie.-polytherblend, as described below:-0 -70% by weight.of -30% by weight-OfStyrene-Butadiene Styrene (Kraton D-1192) o The RCO was heated to 195T under light agitation at which point the D-1i92 S'B:S
-was gradually added and cOntinued to be agitated until a uniform blend was achieved. (approximately 1540 minutes). At this point the elemental sulfur was :added at the equivalent .011/60 of the SBS content for 60 Minutes, after which the reacted blend was cooled.
[00098] :Blend Bisa modified -asphaftbinder comprising:
= 9404-neat asphalt binder graded as PO64.2.2 (PO 65.724.9) by weight of the blend..

6%-ofaleacted thermoplastic polymer blend (Containing 0.0018% sulfur by weight of the asphalt), as described below:
0; .70% by weight ofasuffurized refined soy bean Oil reacted with-TO% by weight of *Mental .sttlftir at 175T for 33 hrs under a Nitrogen sparge.. This resulted in a -modifier with oligomers, blended back with refined SBO to-a-45%
oligomer con cut (VsEK)45).
Q- -304 by weight.ofStyrene,Butadiene Styrene (Kraton D-1192) O --The:VSBO45 was heated to 195 C under light agitationatwhith point the D-SOS was gradually added and continued to be reacted for 60 minutes after which the reacted bleudwas cooled.
Blending Procedure:
1. The oil was blended intathe asphaltafter thebinder had been annealed at 15:0T. fort. hoar (Blend A only); The modified binder heated to about:1.93 C-forpolymer modification, 2. The Rpm in the high shear mixer was set to 1.000 whiledie.SBS WAS. added (withiti 1.
minute). :Immediately after addition of the polymer the RPM was briefly ramped up to 3000 rpm-forapprOtimately 10 minutesto insure full break down oldie SBS pellets, after -which the shearlevel was lowered to 1000 rpm.
3. -Polymer blending AVM continued at 1000 rpm. for a total. of 2 hilt.
4. If* cross linker Step is needed (Blends A and B), the temperature was dropped to 000 182T at a 150 rpm- at which point: the sulfur cross linker was added.
Blendingwas COMittued at 182'C and 150 rpm for 2 hrs.
22.
SUBSTITUTE SHEET (RULE 26) 5. :$4.rtipies wc.k.e..Wken frani thePIyrner inOdified =bitider before..and after :01y0:#1::# 15 0CcirIng. 1r apprOght4iely: 12h rs verntghtoachieve:14a:swefli rig of M=iiiht ti .t i'akt3 :tdgItt0* : AAAnn n*.

f3i,onci Cora-1160ns ....11:ecoverv Cross- at .3.4.'s=(% =
Inf SBS/00 34:-.C, 3.2 Raker TinIQ 3.2 k.Pa =
= Curitlg 'Ratio k-Pa Added.
p664.22+6.0,4(12C0-SBS
NO NO .2 hbistr.... 0,30 0.13 70:30).
No No (L30 0.08 35.26 P044.42 +.6..0%1V$094$135ihoiir __________________________________________ 70:30).
No. (OP
000100] .The:Testilts.=shOWt difference between the iherhithill4tipdaydier,41 blend in ley.hi**.$41:0*,w0:44ded $ep,a4telytct:the.4sPh41:01001., .42.icl :the :pept400$01101000.
pOlyhter.b.1:00d::hase.4.::otthe.use:iif.a.:m4filtized: vegetable oil The iittraeted.tberotopiastit blood thd notathiesie=the.5.4me = e 0004y. .00 1100.brrn anc e Of that of the cc acted hteM1, anti:the:140r the :elmslitticerjhto tg.61itun.w.ti did not p.v.:pNome 01,6: difference in perfomm.ce It ! hud he noted that itie:soitttea the bicete.Wabie oil W.a..4:60:tillfdtetithetWeen Mend..kand 00.!:effe.ct. of wbiekolviot results .01Øproferonce:of the. tisea.o.m.:reaetive .$0:fix ht:thesulturizettvegetahle based oil as..:dv pre-fErred rmethod of auii jag:a reacted Iitlermitifilqstic. pcAymer and biorenewable-Oil.b.1444:
[(4001.01] A sjggi c ant Jib:crease:to elasticity atut=::ereep...stiffrics (rextuctiolyik:crppp.
complimee)vas:bbgervesiwith the.:tigeOf the: teaeted.NeSetable eibSES
diettropiastio polymer n ippitificatiOti,i'Ock0oggtahe ses.,..000.4Ø1Øe.:00fiatt inders remained:.unehange& Purthermore,..use:.of iiwreKtaYcgetab.Wo*S0s:,.theroloptastic polymer imillate0 the need for addtng a sep tc cross ltiiker rh ak$itni fic.aTtOyiltipt'Ø.e arid smrnphy the .z.iipdirtp4tiOp:.prpmfof.the,.etifl:m4erõ:!As: .111gw:c.11.111rqp sulfur) ilteducedto:::tsingit,step modification,witii :erthamed:performancelbat otily-mgditod.
100 diaii:11.41:10:foio:.:btot* time gr:edityetiOtt4t.tilehd*..

SUBSTITUTE SHEET (RULE 26) Example 7: Comparison of Blending, Conditions. for Unreacted Vegetable-based Thermoplastic Poly ers:
[0.00102] Three polymer modified asphalt bleitdaWere -Coin-pared in which tin-reacted SBS-vegetable based oil was use4:as.a thermoplastic polymer replacement and. the only additive.
Blend conditions Were vatted it the BlendS:A, B; and:C in terms of Shearing and blending temperature as well as addition of a cross linker.
[000103] Blend A is a modified asphalt binder that-Wag-manually.
homogenized at 115 C
for 1 minute, comprising:
* 94.0% neat asphalt binder graded as-PG.64-22 (PG 65:7-24.9) by weight Of the blend.
= 6% of .a reacted thermoplasticpolynter blend, as described below:
6- :50% by weight of--RCIP
0_ .50%.by weightofStyrene-Butadiene Styrene-(KratonD,1192) ED The -11.00 was heated to 195 C tinder light agitation at which point the-1),11 92--SBS
was gradually added and continued for. 2 hrs (9001041 'WO Wis a modified asphalt binder -that was high sheatblended at 1-93 C Or 2 hrs, -comprising:
= .9404-neat asphalt binder graded as.11004-22(po 65.7,24.9) by weight of the blend.
6%-oi7A reacted thermoplastic polymer, as described below:
O :50% by weight of RCQ.
= -50% by weight of Styrene-Butadiene Styrene (Kraton 04192) o The R00 Was heated to 195 C under light agitationatwhieb pow the 0-11:92 SIBS
was gradually added and continued for 2 in-s [000105] Blend 0 is:a modified asphalt binder that was high shear blended at 1.93 C-Efor2 hraõ-cornprising:
* 93.95% neat asphalt binder graded as PG6442 (PG:657;.24.9) by weight-of the blend.
= 6% of reacted thermoplastic polymer, as described Into*:
0. 59,4:-.1:1 weight of RCO.
o .50% by weight of Styrene-Butadiene Styrene (Kraton D-1192) o The Ra)waaheated to 195 C under light agitation at which point the 041925-BS
was graduallyadded and continued:for 2 hrg = 0.05% by weight.of elemental sulfur added as a cross-linker.
2.4 SUBSTITUTE SHEET (RULE 26) Muitipk Sfrot-f;cm?p wad Rrory IvOt-wt''porrottuNd yo naga biodet 3."::l tvor4faumw AAM-1 r0 T860. DidAl* ar.*:,36 [01901-0.6] Table 7:
Table 7 Blend-Cenditions Cross,, -Blend itif0 30.t. %Recovery Binder Name 12hr S118../Oil =
at3eC,12 linker 3:2-APa Added Curing Ratio: .kPa .P064-2246-.0%(RCO-SBS =./s2 Nib 2 hours 0,50- 0,10 29.35 -50:50) --Hand Blended at 175 C =
-P-664-22 -46.0%(RCO-SBS
'No 2 hours 050 0,08 32.88 5Q:50) High Shear Blended P064-22-4-6,0%(1WO-SBS
50:50)+-0:05%S., HigliShear :Yes Yes 2 hours 050 005 4Q,12 Blended [000'107] The-results highlight a few important aspects athe invention:
= It was possible to get partial performance from the-thermoplastic-polymer by blending at 175 C at VcryloW shear levels. With COnventional 8BS-ModifitatiOni it is often not possible to get polymer elasticity at temperatures to approximately I arc and without high Shear blending to:initially bit*.dO*nthe polymer:
= The unreacted them plastic polymer blend (Blend :c) did not exhibit the full .performance exhibited by the conventional polymer modification.
= Addition of sulfur to the asphalt blend containing the unreacted thermoplastic -polymer significantly enhanced the-performance beyond that of the:conventional modification without a cross-linker.
to- it is noted as.a reminderthat= example 6 showed that sulfur reaction through the use of theaCtive solftif in the sulfurized vegetable oils resulted in the:highest performing !thermoplastic polymer.
_Example 8: Modified \readable Oil Based Thermoplastic Plastomerie Polymer (MVOTPP) [006110] A. modified:asphalt binder comprising:
-= 96.5% by weig4:pfneat asobAkbin.der graded as pG58--4 (P.0 0. 1.--;9.9) =-= 4..5% by *eight of -a blend comprising:
SUBSTITUTE SHEET (RULE 26) -78% by weight -of a funetiOnaliZed Polyolefin (Titan 7686).
p- 22% by weightof cobalt Catalyzed (500 ppm) Blown. Recovered:Corn Oily 'reaetedatt1PC for9 hrs and having a 24%-oligomettoment.
o; The:polymerized oil was boated to 130 C. under ligbtagitation atwhich point the ;oxidized polyethylene Was gradually added. The reaction was continued for .1-hr.
The end product (referred to herbyas MYOTPP) was-a snit.brittle solid tha.was -:eaSily flaked. Figure 9 shows thelhertiud analysis results for the-end product.
r.ninditier =so0iienileti ene iontialt aft,er the had nnets nmeneleii af.1.50 C i ihelm Fez-An-me gra&
n,e0.-nsern-perfneenini tet ateitedAnix, W.AA$IITO M320, The:
nInctiAlizokinit.Tetnited in:n-4,7'C Inn: enninerMitiNe:grOft irapi-isvemenliõ The. net ettengnin OAn mat inw perforiniinve gre reeiiite0 in 4 8V ry eignirit-ant invenvenseeo Ki-!seted Unvetrallire Inttrynt, nem& ere :etinstitt in [000109) Table $
' .
Binder Name 11 R-DSR DSR BBR- BBR
'5-e Vntrodified 92.0 62.14 62.88 -29.9 -29.9 -445%IvIVOTPP 93.8 59.18 59.5.3 -36.9 [0001101 Thethermoplastic plastomerlepolyrner based on the incorporation of the blown recovered cornoilModifier achieved one low temperature grade improvement While stilt passing -the-PG58: high temperature!grade specification. This is a significant achievement, as end users Will almost tkausivetyl need to use two modifiers, to achieve the low temperature grade improvement-while-maintaining tbe:base high temperature grade.
Example 9: Modified Vegetable Oil Based Thermoplastic PlaStorneric-Polyiner fMVOIPP#1i 1000111] The thermoplastic polymer described in,Th(ample8-(MVOTPP#1) was compared to the unmodified neat asphalt and asphalt Only MOdified with the Titan 7686 Oxidized Polyethylene, The dosage of the-.MVOTPP#1 was 4.5% by Weight of the Modified asphalt.
0. The dosap-ofthefunctionafized pulyolefin (Titan 7686) was 1%
(equivalent :to the dosage used in -the MATOTPPitli: based on the:reaction:charges):
[0991-121 Using a dynamic Shear rheometera stepwise. temperature sweep was performed on each of the described binders. A concentric cylinder geometry-wasused.tofacilitate accurate SUBSTITUTE SHEET (RULE 26) measureinentsIthigh temperatures and low -tiriSeositieS:. Theteniperature was ramped up between 1.5 and 1.50 C. At. 5 C increments .a 1.0minuteequilihration time step was,defined, followed-by loading at 1 Hz at a 1% strain amplitude:froth. which the complex Modulus was derived over the range of temperature steps.. The results are shown in figure 0.
[00OW] The results-shown in figure-1.0-highlight .an. important aspectof the MV(YTPP:, namely the idealeffeqt on the base asphalt modulus across the temperature range of interest in as.ptialtapplications:
= At temperatures between 100 and 159 C., the MVOTPP#. 1 reduced the complex modulus and dynamic viscosity by atinVerage of2&%. This translates-to high potential for-enhancing workability and compaction. Thus the-MVOTPPfil otTers the benefits of a."Compaction AidAdditive"-acthistern.perature- range.
= At. temperatures between 40 and. 100 C, the MVOTP.P#1 :increased the complex .modulus arid-dynamic viscosity byan average of 115%; Thus the MVOTPP#1 behaves as a high temperatureperformance grade modifier at this temperature range.
= At:temperatures lower than 40 C the IVIVOTPP#.1 reduced the complex:
modulus and dynamite viScoSity by an average-of 37% (dOWA tothel-PC measured during :this test).- Thus the MVOTPP41 offers the benefit of a low temperature modifier at:this temperature range.
Example 10: Modified Vegetable Oil Based Thermoplattit-Plastomeric Polymer (MVOTPP#2) [000114) A triaminononane (TAN)Steitrainikwasprodtteed as a thermoplastic pOlymeric wax as. inflows:- Charges were calculated so that: the reaction product will achieve:the desired -whine 00_404-value-Or:id_ value 0'0-5 mg K.QH/g: and amine value. of 0-30.nig-lcOH/g).- The fatty material,.M this! case 4. hydrogenated distillate-from the vegetable.
refining process, was melted in an Wen and charged at a.30643g tol-1-1., flask and a condenserwas setup to condense 'any' waterandfatty distillate cartied over aswell as water from the reaction. The fatty-arid washeated to 106 C under anitrogen.sparge. Once-the flask reached target-temperature 'TAN. (58j6g) was added.slowly via an addition funnel over a half hourm control the resulting exothermic reaction. The reaction:Was then heated to between 160!C and allowedto-react until the acid value leveled within the desired range, indicating the-level of fatty arid containing SUBSTITUTE SHEET (RULE 26) material conSurription..-Thelesidt was a thermoplastic polymer with. a-m elting-point of approximately MT.
(9001.151 A therriMplaStiepOlymer-waadded at a 3% dosage to af)664722hinder. Using a dynamic shear rheometer a step-wise temperature sweep was performed on each fthe described binders.-Atoneentrieqlinder geometry was used to facilitate accurate measurements at high temperatures and low viscosities.. The temperature was ramped up between 1$
and 150 C. At C. increments a 10 311 i n ute equilibration time was defined, fellowed by loading at 1 Hz at a 1% strain amplitude from which the complex:modulus was derived over the range of -teniperaturcittepS,.The reSolts are Iliewnin Figures 11 and 12.
Example 11: Modified Vegetable Oil Based Thet noplaStic-PlastOmeric Polymer (MVOTPP#3) [000110] An ethylene bis-stearam ide(EBS). was prOducedas a thermoplastic polymeric wax as follows:tharges were calculated so that the reaction product will achieve the desired amine and acid-value (Atid. value-Of 0-5 thig-K9Hig and amine Value of 0-30-trig-X-OH/g).- The fattymateriakinthis. case a hydrogenated distillate :from the vegetable refinine process, was melted in an. oven and charged at a 402.7 toa-14..110A -anda condenser was setup to condense any :Water and fatt) ditillatecarried over as well as water from The reaction.
The fatty acid was heated to 100. Clonder a nitrogen sparge: Once the flask reached target:
temperature., Ethylene Diamine (.47;3g) was added slowly via an addition funnel over a halt' hour to control the resulting exotheriniereaction. The reactionwas-then heated to between 170 C.
and allowed to react until-the acid value leveled within the desired range, indicating the level of fittty acid containing material consumption.
[000117] The -thermoplastic polymer Was added at a 3% dosage to a PG.04-22 binder. :The thermoplastic polymer was produced as-described below:-6- -50% by Weight of :Ethylene BiS-Stearatitide (EBS).
p- :$0% by weight of a refined soybean-oil.
b- The oil Was heated to 130 C under light agitation :at which -point the EBS
WAS
gradually added. The reaction was continued for I hr. The end product (referred to herby as MVOTPP#3) was a soft brittle Solid that was easily naked.
[0001:18] Using a dynamic. shear rheometera step-wise temperature swimi:waSPerformed on each of described bindersõk concentric cylinder geometry was used to:facilitate-accurate ineasureMents at high temperatures and low viscosities. The temperature Was ramped up between :15 and 150 C At .5 C increments a 10 minute equilibration time step was defined, SUBSTITUTE SHEET (RULE 26) fotiovstd: by loading at I Hz al a I% straihltfhpl bide from which the ebruplek wiit4 .06.vc4 over the range. oftemperange: .steps. The :mantis. are$hoyvn. In Figure 79.
SUBSTITUTE SHEET (RULE 26)

Claims (92)

1. A polymeric composition, comprising a random copolymer comprising three or more distinct monomers, wherein a first monomer is a biorenewable oil and a second monomer is a thermoplastic polymer.

2. The polymeric composition of claim 1, wherein the biorenewable oil has been cationically polymerized using Bronsted acids and Lewis acids.

3. The polymeric composition of Claim 1, wherein the biorenewable oil has been polymerized using oxidation, super acid catalysis, bodying, or sulfurization techniques, or a combination thereof.

4. The polymeric composition of claim 1, wherein the copolymer is hyperbranched.

5. The polymeric composition of claim 1, wherein at least one monomer is sulfur.

6. The polymeric composition of claim 1, wherein at least one monomer is a vinylaromatic compound.

7. The polymeric composition of claim 1 wherein at least one monomer is styrene, butadiene, indene, divinylbenzene, or an alpha-olefin.

8.The polymeric composition of claim 1, for use in asphalt applications such as compaction aid additives, rheology modifiers for enhanced high and low temperature asphalt performance, rheology modifier with enhanced storage stability, rheology modifier with enhanced oxidative aging stability, compaction aid additive rheology modifier for enhanced low temperature performance while minimizing reduction in modulus at high temperature performance ranges, rejuvenator agent, recycling agent, and any combination thereof.

9. The polymeric composition of claim 1, for use in hot mix, warm mix, and cold mix asphalt applications, roofing asphalt and coatings.

10. A polymeric composition, comprising a biorenewable oil and a thermoplastic polymer, wherein the thermoplastic polymer comprises about 1-75 wt% of the polymeric composition with a remaining balance of a biorenewable oil.

11. The polymeric composition of claim 10, wherein the thermoplastic polymer is an elastomer, a plastomer, a pre-polymer, an oligomer, or a high-molecular weight polymer.

12. The polymeric composition of claim 10, wherein the thermoplastic polymer is a polyolefin.

13. The polymeric composition of claim 10, wherein thermoplastic polymer is ground tire rubber.

14. The polymeric composition of claim 10, wherein the thermoplastic polymer is a styrene based copolymer.

15. The polymeric composition of claim 14, wherein the styrene based copolymer is a styrene-butadiene block copolymer.

16. The polymeric composition of claim 10, wherein the biorenewable oil is a plant-based, animal-based, or microbial-based oil.

17. The polymeric composition of claim 10, wherein the biorenewable oil is recovered corn oil or soybean oil.

18. The polymeric composition of claim 10, wherein the biorenewable oil is partially or fully hydrogenated oils, oils with conjugated bonds,or bodied oils wherein a heteroatom is not introduced.

19. The polymeric composition of claim 10, wherein the biorenewable oil is a previously modified, polymerized, or functionalized oil.

20. The polymeric composition of claim 10, wherein the biorenewable oil is at least partially sulfurized.

21. The polymeric composition of claim 10, further comprising a cross-linking agent,

22. The polymeric composition of claim 21, wherein the cross-linking agent is a sulfur containing compound or a peroxide.

23. The polymeric composition of claim 21, wherein the cross-linking agent is a sulfur containing compound and a compound selected from the group consisting of peroxide, polyphosphoric acid, and super acid catalysts.

24. The polymeric composition of claim 10, wherein the bioreneweable oil is cationically polymerized.

25. The polymeric composition of claim 10, wherein the biorenewable oil is polymerized through oxidation, super acid catalysis, bodying, or sulfurization, or a combination thereof.

26. The polymeric composition of claim 10, for use in asphalt applications such as compaction aid additives, rheology modifiers for enhanced high and low temperature asphalt performance, theology modifier with enhanced storage stability, rheology modifier with enhanced oxidative aging stability, compaction aid additive rheology modifier for enhanced low temperature performance while minimizing reduction in modulus at high temperature performance ranges, rejuvenator agent, recycling agent, and any combination thereof.

27. The polymeric composition of claim 10, for use in hot mìx, warm mix, and cold mix asphalt applications, roofing asphalt, and coatings.

28. A modified asphalt, comprising:
an asphalt binder in an amount ranging front about 60-99.9 wt%;
an asphalt modifier in an amount ranging from about 0.1-40 wt%; wherein the asphalt modifier comprises:
about 1-75 wt% of a thermoplastic polymer and a remaining balance of biorenewable oil.

29. The modified asphalt of claim 28, wherein the thermoplastic polymer is a polyolefin.

30. The modified asphalt of claim 28,wherein the thermoplastic polymer is a styrene based copolymer.

31. The modified asphalt of claim 30, wherein the styrene based copolymer is a styrene-butadiene block copolymer

32. The modified asphalt of claim 28, wherein the biorenewable oil is a plant-based, animal-based, or microbial-based oil.

33. The modified asphalt of claim 28, wherein the biorenewable oil is recovered corn oil or soybean oil.

34. The modified asphalt of claim 28, wherein the biorenewable oil is partially or fully hydrogenated oils, oils with conjugated bonds, or bodied oils wherein a heteroatom is not introduced.

35. The modified asphalt of claim 28, wherein the biorenewable oil is a previously modified, polymerized, or functionalized oil:

36. The modified asphalt of claim 28, wherein the biorenewable oil is at least partially sulfurized.

37. The modified asphalt of claim 28, wherein the asphalt modifier further comprises a cross-linking agent.

38. The modified asphalt of claim 37, wherein the cross-linking agent is a sulfur containing compound or a peroxide.

39. The modified asphalt of claim 37, wherein the cross-linking agent is a sulfur containing compound and a compound selected from the group consisting of peroxide, polyphosphoric acid, and super acid catalysts.

40. The modified asphalt of claim 28, wherein the bioreneweable oil is cationically polymerized.

41. The modified asphalt of claim 28, wherein the biorenewable oil is polymerized through oxidation, super acid catalysis, bodying, or sulfurization, or a combination thereof.

42. A method of making a modified asphalt, comprising:
a. manufacturing an asphalt modifier, comprising:
i. heating a vulcanized biorenewable oil to a temperature exceeding that of the thermoplastic polymer's melting point;
ii. adding the thermoplastic polymer to the biorenewable oil and iii. agitating the thermoplastic polymer with the biorenewable oil to obtain a homogeneous blend ;
b. blending the asphalt modifier into an asphalt binder.

43. The method of claim 42, wherein the modified asphalt comprises 0.1-40 wt% of the asphalt modifier and 60-99.9 wt%-of the asphalt binder.

44. The method of claim 43, wherein a crosslinker agent is not required to deliver equal or better elasticity of conventional asphalt polymer modification procedures.

45. The method of claim 42, wherein step (b) takes at least 30% less blending time than conventional asphalt polymer modification procedures and delivers equal or better elasticity.

46. The method of claim 42, wherein step (b) takes at least 40% less blending time than conventional asphalt polymer modification procedures and delivers equal or better elasticity.

47. The method of claim 42, wherein step (b) takes at least 50% less blending time than conventional asphalt polymer modification procedures and delivers equal or better elasticity.

48. The method of claim 42, wherein step (b) takes at least 60% less blending time than conventional asphalt polymer modification procedures and delivers equal or better elasticity.

49. The method of claim 42, wherein the temperature during step (b) is at least 5°C below temperatures used in conventional asphalt polymer modification procedures.

50. The method of claim 42, wherein the temperature during step (b) is at least 10°C below temperatures used in conventional asphalt polymer modification procedures.

51. The method of claim 42, wherein the temperature during step (b) is at least 15°C below temperatures used in conventional asphalt polymer modification procedures.

52. The method of claim 42, wherein the temperature during step (b) is at least 20°C below temperatures used in conventional asphalt polymer modification procedures.

53. The method of claim 42, wherein the temperature during step (b) is at least 50°C below temperatures used in conventional asphalt polymer modification procedures.

54. The method of claim 42, wherein an additional curing step after step (b) is not required.

55. The method of claim 42, further comprising curing the asphalt modifier after step (b).

56. The method of claim 55, wherein the curing time is reduced by at least 60%. compared to conventional asphalt polymer modification procedures.

57. The method of claim 55, wherein the curing time is reduced by at least 70% compared to conventional asphalt polymer modification procedures.

58. The method of claim 55, wherein the curing time is reduced by at least 80% compared to conventional asphalt polymer modification procedures.

59. A method of making a modified asphalt, comprising simultaneously blending a biorenewable oil and a thermoplastic polymer into an asphalt binder, wherein the biorenewable oil and the thermoplastic polymer together are an asphalt modifier.

60. The method of claim 59, wherein the modified asphalt comprises 0.1-40 wt% of the asphalt modifier and 60-99.9 wt.% of the asphalt binder.

61. The method of claim 59, wherein the blending takes at least 30% less blending time than conventional asphalt polymer modification procedures and delivers equal or better elasticity.

62. The method of claim 59, wherein the blending takes at least 40% less blending time than conventional asphalt polymer modification procedures and delivers equal or better elasticity.

63. The method of claim 59, wherein the blending takes at least 50% less blending time than conventional asphalt polymer modification procedures and delivers equal or better elasticity.

64. The method of claim 59, wherein the temperature during blending is at least 5°C below temperatures used in conventional asphalt polymer modification procedures.

65. The method of claim 59, wherein the temperature during blending is at least 10°C below temperatures used in conventional asphalt polymer modification procedures.

66. The method of claim 59, wherein the temperature during blending is at least 15°C below temperatures used in conventional asphalt polymer modification procedures.

67. The method of claim 59, wherein the temperature during blending is at least 20°C below temperatures used in conventional asphalt polymer modification procedures.

68. The method of claim 59, wherein the temperature during blending is at least 50°C below temperatures used in conventional asphalt polymer modification procedures.

69. The method of claim 50, wherein an additional curing step after blending is not required.

70. The method of claim 59, further comprising curing the asphalt modifier after blending.

71. The method of claim 70, wherein the curing time is reduced by at least 60% compared to conventional asphalt polymer modification procedures.

72. The method of claim 70, wherein the curing time is reduced by at least70% compared to conventional asphalt polymer modification procedures.

73. The method of claim 70, wherein the curing time is reduced by at least 80% compared to conventional asphalt polymer modification procedures.

74. The method of claim 59, further comprising adding a crosslinking agent to the asphalt binder.

75. The method of claim 74, wherein the crosslinking agent is a sulfur-containing compound.

76. The method of claim 74, wherein less than half of the amount of crosslinking agent is used compared to conventional asphalt polymer modification procedures.

77. A method of making a modified asphalt, comprising simultaneously blending a vulcanized biorenewable oil and a thermoplastic polymer into an asphalt binder, wherein the vulcanized biorenewable oil and the thermoplastic polymer together are an asphalt modifier.

78. The method of claim 77, wherein the asphalt modifier comprises 3 or more distinct monomers.

79. The method of claim 77, wherein the modified asphalt comprises 0.1-40 wt% of the asphalt modifier and 60-99.9 wt% of the asphalt binder.

80. The method of claim 77, wherein the blending takes at least 30% less blending time than conventional asphalt polymer modification procedures and delivers equal or better elasticity.

81. The method of claim 77, wherein the blending takes at least 40% less blending time than conventional asphalt polymer modification procedures and delivers equal or better elasticity.

82. The method of claim 77, wherein the blending takes at least 50% less blending time than conventional asphalt polymer modification procedures and delivers equal or better elasticity.

83. The method of claim 77 wherein the temperature during blending is at least 5°C below temperatures used in conventional asphalt polymer modification procedures.

84. The method of claim 77, wherein the temperature during blending Is at least 10°C below temperatures used in conventional asphalt polymer modification procedures.

85. The method of claim 77, wherein the temperature during blending is at least 15°C below temperatures used in conventional asphalt polymer modification procedures.

86. The method of claim 77, wherein the temperature during blending is at least 20°C below temperatures used in conventional asphalt polymer modification procedures.

87. The method of claim 77, wherein the temperature during blending is at least 50°C below temperatures used in conventional asphalt-polymer modification procedures.

88. The method of claim 77, wherein an additional curing step after blending is not required.

89. The method of claim 77, further comprising curing the asphalt modifier after blending.

90. The method of claim 89, wherein the curing time is reduced by at least 60% compared to conventional asphalt polymer modification procedures.

91. The method of claim 89, wherein the curing time is reduced by at least 70% compared to conventional asphalt polymer modification procedures.

92. The method of claim 89, wherein the curing time is reduced by at least 80% compared to conventional asphalt polymer modification procedures.